US4943617A

US4943617A - Liquid crystalline copolymer

Info

Publication number: US4943617A
Application number: US07/091,667
Authority: US
Inventors: Karl-Heinz Etzbach; Bernd Hisgen
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1986-09-19
Filing date: 1987-09-01
Publication date: 1990-07-24
Anticipated expiration: 2007-09-01
Also published as: EP0260687A2; DE3631841A1; DE3775313D1; EP0260687B1; EP0260687A3; JPS6377910A

Abstract

A liquid crystalline copolymer contains a comonomer to which a radical ##STR1## is bonded, where X is a chemical bond, O or NR¹, Y is a chemical bond or --CO--, R¹ is hydrogen or C₁ -C₄ -alkyl and A is a linear or branched C₂ -C₂₀ -alkylene group which may be interrupted by --O-- or ##STR2## The liquid crystalline copolymers have very good lightfastness, high dichroism and a high absorption.

Description

The prior art discloses polymers which have liquid crystalline properties and in which the radicals leading to the meso phase are bonded to the polymer main chain via flexible spacers, as side chains.

An overview is given in, for example, Liquid Crystal Polymers I-III in Adv. Polym. Sci. 59-61, M. Gordon and N. A. Plate, Springer-Verlag, 1984, Berlin.

Suitable polymer main chains are polyacrylates or polymethacrylates (e.g. DE-A No. 27 22 589) or polysiloxanes (EP-A No. 29 162).

Compared with low molecular weight liquid crystals, these polymers have the advantage that the structure remains unchanged during the transition from the liquid crystalline phase to the solid phase, permitting freezing of a liquid crystalline structure in the glassy state.

Copolymers having mesogenic groups and dye radicals in the side chain are described in EP-A No. 90 282 and can be used in electrooptical displays or for information storage (EP-A No. 171 045). For these applications, it is important that the properties of the dyes are optimized for the particular use.

It is an object of the present invention to provide liquid crystalline copolymers which carry a dye radical having high dichroism, very good lightfastness and a high molar extinction. The absorption maximum of the dye should be in the range of the He-Ne laser emission (633 nm).

We have found that this object is achieved by the liquid crystalline copolymers according to the invention. Accordingly, the present invention relates to a liquid crystalline copolymer which contains, as copolymerized units, a comonomer which carries a dye-containing radical of the general formula ##STR3## where X is a chemical bond, --O-- or --NR¹, Y is a chemical bond or --CO--, R¹ is hydrogen or C₁ -C₄ -alkyl and A is a linear or branched C₂ -C₂₀ -alkylene group, and the carbon chain of the alkylene group can be interrupted by --O-- or

The novel copolymers can be used in particular together with low molecular weight liquid crystals or liquid crystal mixtures in electrooptical displays of the guest-host type and serve in this respect as solubilizers for the dye. Compared with the blue dyes described in EP-A No. 90 282, the dye radical present in the novel copolymers has the advantage of very good lightfastness coupled with high dichroism. Furthermore, the molar extinction coefficient ε is substantially higher than in the case of the 1,4-diaminoanthraquinones of EP-A No. 90 282.

The novel copolymers can contain up to 45% by weight, based on the copolymer, of a dye. As a rule, the dye content is from 0.5 to 40, preferably from 0.8 to 30%, by weight, based on the copolymer. Another important technical use of the copolymers according to the invention is for information storage. Since very high absorption storage in a very thin polymer layer (generally about 0.1-1 μm) is required here, a very high molar extinction coefficient is a technical advantage. Moreover, the absorption maximum of the novel dye system used is tailored to the He-Ne laser emission.

Suitable liquid crystalline polymers are those which carry a mesogenic group R³ bonded to the main chain via a spacer. The spacer serves here for decoupling the mesogenic group from the main chain and permits independent movement of the mesogenic group. A preferrred spacer A is a linear or branched C₂ -C₂₀ -alkylene group, which may be interrupted by --O-- or ##STR4##

Mesogenic groups R³ are mentioned, inter alia, in Kelker and Hatz, Handbook of Liquid Crystals, Verlag Chemie 1980, pages 87-113.

Preferred liquid crystalline copolymers are those of the general formula ##STR5## where R² is hydrogen, methyl or chlorine, X is --O-- or ##STR6## Y is a chemical bond or --CO--, R¹ is hydrogen or C₁ -C₄ -alkyl, A is a linear or branched C₂ -C₂₀ -alkylene group which may be interrupted by --O-- or ##STR7## and R³ is a mesogenic group, and the copolymer may carry identical or different mesogenic groups.

Specific examples of A are --(CH₂)₂ --, --(CH₂)₃ --, --(CH₂)₄ --, --(CH₂)₅ --, --(CH₂)₆ --, --(CH₂)₇ --, --(CH₂) ₈ --, --(CH₂)₉ --, --(CH₂)₁₀ --, --(CH₂)₁₁ --, --(CH₂)₂ --O--(CH₂) ₂ --, ##STR8##

Y is preferably a chemical bond.

Examples of mesogenic groups R³ are: ##STR9## where Y¹ is --O--, ##STR10## or --S--, Z is a chemical bond or a radical of the formula ##STR11## U is a chemical bond or a radical of the formula ##STR12## R⁵ is hydrogen, C₁ -C₁₂ -alkyl, C₅ -C₇ -cycloalkyl, C₁ -C₁₂ -alkoxy, C₄ -C₁₂ -alkoxycarbonyl, C₁ -C₁₂ -alkanoyloxy, fluorine, chlorine, bromine, cyano, phenyl, 4-cyanophenyl or nitro, R⁶ is hydrogen, C₁ -C₁₂ -alkyl, C₁ -C₁₂ -alkoxy or C₁ -C₁₂ -alkoxycarbonyl and R⁷ is methyl, ethyl, methoxy, ethoxy or chlorine.

Particularly preferred liquid crystalline copolymers of the general formula (II) are those where R² is hydrogen or methyl, X is --O--, Y is a chemical bond, A is a linear C₂ -C₂₀ -alkylene group, R³ is ##STR13## R⁵ is C₁ -C₁₂ -alkyl, C₁ -C₁₂ -alkoxy, C₄ -C₁₂ -alkoxycarbonyl, C₁ -C₁₂ -alkanoyloxy, fluorine, chlorine, cyano, phenyl, 4-cyanophenyl or nitro and R⁶ is C₁ -C₁₂ -alkyl.

Further examples are liquid crystalline polymers of the general formula (III) ##STR14## where A and R³ have the meanings given above, X¹ is a chemical bond and R⁴ is ethyl, propyl, butyl, phenyl or, preferably, methyl.

Liquid crystalline copolymers which contain optically active groups are also important. The optically active groups may be present in the spacer A or in the radical R³, in the latter case preferably in the radicals R⁵ or R⁶.

Specific examples of optically active groups are ##STR15##

Such copolymers can form cholesteric or chiral smectic phases.

The copolymers can be prepared by conventional methods usually employed in polymer chemistry.

The novel polyacrylates and polymethacrylates can be prepared, for example, by copolymerizing the monomers ##STR16## by a conventional method.

The synthesis of the mesogenic monomers is described, for example, in German Laid-Open Application DOS No. 2,722,589 or by V. P. Shibaev et al. in Eur. Polym. J. 18 (1982), 651-659.

The novel polyacrylates and polymethacrylates can also be prepared by introducing the radicals X--A--R³ and X--A--dye into polymeric compounds of the formula ##STR17## where T is an exchangeable radical, for example chlorine or lower molecular weight alkoxy, by esterification, transesterification or amidation by a conventional method (C. M. Paleos et al. in J. Polym. Sci. Polym. Chem. Ed. 19 (1981), 1427).

The alkylation of the polymeric compounds of the formula ##STR18## with halides of the formula Hal--A--R³ and Hal--A--dye (where Hal is Cl, Br or I) is also possible and is carried out by a conventional method (P. Keller in Macromolecules 17 (1984), 2937-2939).

The novel dye-containing polysiloxanes can be prepared by processes similar to those described in EP-A No. 29 162 or EP-A No. 60 335 or by introducing mesogenic groups R³ and the dye radical ##STR19## into polymeric compounds of the formula ##STR20## where X, A and R⁴ have the abovementioned meanings and T is an exchangeable or reactive radical, for example Cl, Br, COOH, COCl or CO₂ -alkyl, by etherification, esterification or transesterification by conventional methods.

Details of the preparation are given in the Examples.

A. Synthesis of the dye monomers ##STR21## (a) Preparation of 11-bromoundecyl acrylate

A solution of 50.2 g of 11-bromoundecanol, 72 g of acrylic acid, 3 g of p-toluenesulfonic acid and 0.1 g of hydroquinone in 120 ml of 1,1,1-trichloroethane is heated at the boil for 4 hours under a water separator. After the solution has cooled, it is extracted by shaking with warm water, then with an aqueous sodium bicarbonate solution and then again with water and is dried over sodium sulfate. Thereafter, the solvent is stripped off under reduced pressure in a rotary evaporater and the remaining oil is distilled under greatly reduced pressure. 45.1 g (75% of theory) of a colorless oil of boiling point 113° C./0.2 mbar are obtained.

(b) Preparation of 4,8-diamino-1,5-dihydroxy-3-(4-hydroxyphenyl)-anthraquinone

120 g of 4,8-diamino-1,5-dihydroxyanthraquinone-2,6-disulfonic acid are added to a solution of 60 g of boric acid in 1200 ml of sulfuric acid at 70° C., and the mixture is then stirred for 1 hour at 70° C. The deep blue solution is cooled to 5° C., after which 52.6 parts of phenol are introduced a little at a time so that the temperature does not exceed 5° C. When the addition is complete, the mixture is stirred for a further 2 hours at 5° C. and then added to 4 kg of ice water. The resulting suspension is heated at the boil for a further 4 hours and, after the mixture has cooled, the precipitate is filtered off under suction and washed with water.

The moist residue is dissolved in a mixture of 360 ml of concentrated ammonia and 800 ml of water, after which 66 g of sodium dithionite are added a little at a time and the reaction mixture is stirred for 5 hours at 80°-90° C. After the mixture has cooled, 11.2 g of sodium hydroxide are added and air is passed through the mixture overnight. Thereafter, the mixture is acidified with dilute hydrochloric acid, and the precipitate is filtered off under suction, washed with water and dried to give 61 g (60% of theory) of a crude product, which is purified by recrystallization from 600 ml of nitrobenzene. Mp. 321° C.

(c) Preparation of 4,8-diamino-1,5-dihydroxy-3-(4-(11-propenoyloxyundecyloxy)-phenyl)-anthraquinone.

A mixture of 7.2 g of 4,8-diamino-1,5-dihydroxy-3-(4-hydroxyphenyl)-anthraquinone, 6.7 g of 11-bromoundecyl acrylate, 2.8 g of potassium carbonate, 0.5 g of potassium iodide and 80 ml of dimethylformamide is stirred for 7 hours at 80° C., poured onto ice water and acidified slightly with dilute hydrochloric acid, and the precipitate is filtered off under suction, washed with water and dried to give 11.8 g of crude product, which is purified by chromatography over silica gel (Merck, Kieselgelb 60, 0.063-0.200 mm) using 10:1 tolune/tetrahydrofuran as an eluent, followed by recrystallization from toluene. Mp. 135° C., λ_max (CH₂ Cl₂): 623 nm (27,470) C₃₄ H₃₈ N₂ O₇ (586) calculated: 69.6% C, 6.5% H, 4.8% N, 19.1% O, Found: 69.5% C, 6.6% H, 4.7% N, 18.9% O.

The dyes of Examples 2 to 7 are prepared by a method similar to that described in Example 1, by alkylation of 4,8-diamino-1,5-dihydroxy-(4-hydroxyphenyl)anthraquinone with the appropriate halides.

______________________________________                                    
 ##STR22##                                                                
Example                  Mp.                                              
______________________________________                                    
        ##STR23##        136° C. (from toluene)                    
3                                                                         
        ##STR24##        164° C. (from toluene)                    
4                                                                         
        ##STR25##        136° C. (from toluene)                    
5      (CH.sub.2).sub.9CHCH.sub.2                                         
6      (CH.sub.2).sub.11OH                                                
                         175° C. (from methyl-                     
                         glycol)                                          
7      (CH.sub.2).sub.6Br                                                 
______________________________________

Table 1 shows the order S measured in commercial displays (polyimide orientation) at room temperature at ZLI 1840 (E. Merck), the absorption maximum λ_max and the solubility L measured at room temperature at ZLI 1840 for the dye-containing monomers of Examples 1 to 3.

              TABLE 1                                                     
______________________________________                                    
Example  Order S      λ.sub.max                                    
                              Solubility L                                
______________________________________                                    
1        0.71         642 nm  1.3%                                        
2        0.70         641 nm  3.2%                                        
3        0.68         641 nm  1.1%                                        
______________________________________

B. Synthesis of the copolymers

Polyacrylates, polymethacrylates and polychloroacrylates are prepared by the following general method.

General polymerization method:

In a swinging vessel, azobisisobutyronitrile is added to a monomer solution consisting of 10% by weight of a mixture of dye monomer and mesogenic monomer in absolute tetrahydrofuran or absolute dioxane. Nitrogen is passed through for 10 minutes, after which the monomer solution is thermostated at 60° C. (tetrahydrofuran) or 70° C. (dioxane). When polymerization is complete, the polymers are separated from the monomers by exclusion chromatography over the system Sephadex LH 20/tetrahydrofuran. After the tetrahydrofuran has been removed, the polymer is dried under greatly reduced pressure. The quantitative composition of the copolymers is determined by UV spectroscopy and elemental analysis. The phase transition temperatures are determined by differential calorimetry. The liquid crystalline phases are assigned on the basis of the textures observed under a polymerization microscope equipped with a heating stage. ##STR26##

The copolymers of 4-(6-propenoyloxy)-alkoxy-4'-cyanobiphenyl and 4,8-diamino-1,5-dihydroxy-3-(4-(11-propenoyloxyalkoxy)-phenyl)-anthraquinone were prepared in dioxane by the general method, the amount of dye monomers being varied. The polymers purified according to the stated method form smectic and nematic textures when heated on the heating stage of the polarization microscope.

Table 2 summarized the dye contents of the copolymers, together with the results of the investigations by differential calorimetry and under the polarization microscope (g: glassy, s: smectic, n: nematic, i: isotropic).

                                  TABLE 2                                 
__________________________________________________________________________
                         Mesog.    Dye Dye         Phase                  
                    Initiator                                             
                         monom.    monom.                                 
                                       content     transitions            
Example   k l       (mol %)                                               
                         (g)       (g) (% by wt.)  (°C.)           
__________________________________________________________________________
8a        2 6       1    1.96      0.04                                   
                                       2           g 53 n 108 i           
8b        5 6       1    1.80      0.20                                   
                                       10          g 48 s 103 n 111 i     
8c        6 6       5    1.96      0.04                                   
                                       2           g 41 s 111 n 123 i     
8d        6 6       1    2.94      0.06                                   
                                       2           g 40 s 117 n 127 i     
8e        6 6       1    2.70      0.30                                   
                                       10          g 42 s 116 n 123 i     
8f        6 6       1    2.55      0.45                                   
                                       14.8        g 43 s 146 n 119 i     
8g        6 11      3    1.96      0.04                                   
                                       2           g 40 s 117 n 128 i     
8h        6 11      3    2.70      0.30                                   
                                       10          g 42 s 115 n 125 i     
8i        6 11      3    1.70      0.30                                   
                                       14.5        g 43 s 114 n 123 i     
8k        6 11      3    3.20      0.80                                   
                                       19          g 45 s 112 n 119 i     
Example 9                                                                 
 ##STR27##                                                                
__________________________________________________________________________

The copolymers of 4'-cyanophenyl 4-(6-propenoyloxy)-hexyloxybenzoate and 4,8-diamino-1,5-dihydroxy-3-(4-(11-propenoyloxyundecyloxy)-phenyl)-anthraquinone were prepared in dioxane using 3 mol % of AIBN, by the general method, the amount of dye monomer being varied. The polymers form nematic textures.

Table 3 summarizes the dye contents of the copolymers, together with the results of the investigations by differential calorimetry and under the polymerization microscope (g: glassy, n: nematic, i: isotropic).

                                  TABLE 3                                 
__________________________________________________________________________
                Mesogenic                                                 
                      Dye              Dye         Phase                  
                monomer                                                   
                      monomer          content     transitions            
Example         (g)   (g)              (% by wt.)  (°C.)           
__________________________________________________________________________
9a              1.96  0.04             2           g 33 n 128 i           
9b              1.80  0.20             10          g 33 n 118 i           
9c              3.20  0.80             19.5        g 35 n 109 i           
9d              3.00  1.00             24          g 36 n 106 i           
EXAMPLE 10                                                                
 ##STR28##                                                                
__________________________________________________________________________

The copolymers of 4'-methoxyphenyl 4-(6-propenoyl-oxy)-hexyloxybenzoate and 4,8-diamino-1,5-dihydroxy-3-(4-(11-propenoyloxyundecyloxy)-phenyl)-anthraquinone were prepared in dioxane using 3 mol % of AIBN, by the general method, the amount of dye monomer being varied. The polymers form smectic and nematic phases.

Table 4 summarizes the dye contents of the copolymers, together with the results of the investigations by differential calorimetry and under the polymerization microscope (g: glassy, s_A : smectic A, n: nematic, i: isotropic).

                                  TABLE 4                                 
__________________________________________________________________________
          Mesogenic                                                       
                Dye        Dye   Phase                                    
          monomer                                                         
                monomer    content                                        
                                 transitions                              
Example   (g)   (g)        (% by wt.)                                     
                                 (°C.)                             
__________________________________________________________________________
10a       3.92  0.08       2     g 30 s.sub.A 94 n 117 i                  
10b       3.60  0.40       9.8   g 32 s.sub.A 91 n 111 i                  
10c       3.20  0.80       19.3  g 33 s.sub.A 87 n 105 i                  
__________________________________________________________________________
EXAMPLE 11                                                                
 ##STR29##                                                                
EXAMPLE 12                                                                
 ##STR30##                                                                
EXAMPLE 13                                                                
 ##STR31##                                                                
EXAMPLE 14                                                                
 ##STR32##                                                                
EXAMPLE 15                                                                
 ##STR33##                                                                
EXAMPLE 16                                                                
 ##STR34##                                                                
EXAMPLE 17                                                                
 ##STR35##                                                                
EXAMPLE 18                                                                
 ##STR36##                                                                
__________________________________________________________________________

The polymerization conditions and the results of the investigations for Examples 11-18 are summarized in Table 5:

                                  TABLE 5                                 
__________________________________________________________________________
                  Mesog. Dye  Dye     Phase                               
             Initiator                                                    
                  monom. monom.                                           
                              content transitions                         
Example                                                                   
     Solvent (mol %)                                                      
                  (g)    (g)  (% by wt.)                                  
                                      (°C.)                        
__________________________________________________________________________
11a  dioxane 3    1.98   0.02 1       g 3 n 31 i                          
11b  "       3    1.95   0.05 2.5     g 1 n 28 i                          
12   "       1    3.92   0.08 2       g 12 s 91 i                         
13   "       1    3.92   0.08 2       g 28 n 153 i                        
14   "       1    1.96   0.04 2       g 33 s 90 i                         
15   "       1    2.94   0.06 2       g 88 n 106 i                        
16   "       1    2.94   0.06 2       g 43 n 109 i                        
17   "       3    1.96   0.04 2       g 33 s 98 i                         
18   "       2    4.50   0.50 10                                          
__________________________________________________________________________
EXAMPLE 19                                                                
 ##STR37##                                                                
__________________________________________________________________________

The copolymer of 1.8 g (45 parts by weight) of 4'-cyanophenyl 4-(6-propenoyloxy)-hexyloxybenzoate, 1.8 g (45 parts by weight) of 4-(6-propenoyloxy)-hexyloxy-4'-cyanobiphenyl and 0.40 g (10 parts by weight) of 4,8-diamino-1,5-dihydroxy-3-(4-(11-propenoyloxyundecyloxy) -phenyl)-anthraquinone was prepared in dioxane using 3mol % of AIBN, by the general method. The copolymer has the following phase behavier: g 35 s 110 n 118 i (temperatures in °C.: g: glassy, s: smectic, n: nematic, i: isotropic). ##STR38##

The polymerization conditions and the results of the investigations for Examples 20-24 are summarized in Table 6:

                                  TABLE 6                                 
__________________________________________________________________________
               Mesog.                                                     
                    Dye  Dye   Phase                                      
          Initiator                                                       
               monom.                                                     
                    monom.                                                
                         content                                          
                               transitions                                
Example                                                                   
     Solvent                                                              
          (mol %)                                                         
               (g)  (g)  (% by wt.)                                       
                               (°C.)                               
__________________________________________________________________________
20a  toluene                                                              
          1    9    1    10.3  g 56 n 111 i                               
20b  toluene                                                              
          2    8    2    19.1  g 60 n 109 i                               
21a  toluene                                                              
          2    9    1    9.7   g 58 n 87 i                                
21b  toluene                                                              
          2    2.4  0.6  19.7  g 66 n 87 i                                
22   toluene                                                              
          1    9    1    9.4   g 80 s 169 i 180 i                         
23   toluene                                                              
          3    8    2    18    g 59 s 300 i                               
24   THF  2    4.86 0.97 18.9                                             
__________________________________________________________________________

Claims

We claim:

1. A liquid crystalline copolymer which contains, as copolymerized units, a comonomer of the formula: ##STR39## where X is a chemical bond, --O-- or ##STR40## wherein R¹ is hydrogen or C₁ -C₄ -alkyl, Y is a chemical bond or --CO--, A is a linear or branched C₂ -C₂₀ -alkylene group where the carbon chain of the alkylene group can be interrupted by --O-- or ##STR41## R² is hydrogen, methyl or chlorine and R³ is a mesogenic group of the formula: ##STR42## in which Y¹ is --O--, ##STR43## or --S--, Z is a chemical bond or a radical of the formula ##STR44## --CH═CH--, --N═N, ##STR45## --N═CH-- or --CH═N--, U is a chemical bond or radical of the formula: ##STR46## R⁵ is hydrogen, C₁ -C₁₂ -alkyl, C₅ -C₇ -cycloalkyl, C₁ -C₁₂ -alkoxy, C₄ -C₁₂ -alkoxycarbonyl, C₁ -C₁₂ -alkanoyloxy, fluorine, chlorine, bromine, cyano, phenyl, 4-cyanophenyl or nitro, R⁶ is hydrogen, C₁ -C₁₂ -alkyl, C₁ -C₁₂ -alkoxy or C₁ -C₁₂ -alkoxycarbonyl and R⁷ is methyl, ethyl, methoxy, ethoxy or chlorine.

2. A liquid crystalline copolymer as claimed in claim 1 wherein A is a group of the formula --(CH₂)₂ --, --(CH₂)₃ --, --(CH₂)₄ --, --(CH₂)₅ --, --(CH₂) ₆ --, --(CH₂)₇ --, --(CH₂)₈ --, --(CH₂)₉ --, --(CH₂)₁₀ --, --(CH₂)₁₁ --, --(CH₂) ₂ --O--, --(CH₂)₂ --, --(CH₂)₃ --O--(CH₂)₂ --, ##STR47##

3. A liquid crystalline copolymer as claimed in claim 1, wherein, in the formula, R² is hydrogen or methyl, X is --O--, Y is a chemical bond, A is a linear C₂ -C₂₀ -alkylene group and R³ is ##STR48## where R⁵ is C₁ -C₁₂ -alkyl, C₁ -C₁₂ -alkoxy, C₄ -C₁₂ -alkoxycarbonyl, C₁ -C₁₂ -alkanoyloxy, fluorine, chlorine, cyano, phenyl, 4-cyanophenyl or nitro and R⁶ is C₁ -C₁₂ -alkyl.

4. A liquid crystalline copolymer as claimed in claim 1, which contains from 0.5 to 40% by weight, based on the copolymer, of a dye containing radical.

5. A liquid crystalline copolymer as claimed in claim 2, which contains from 0.5 to 40% by weight, based on the copolymer, of a dye containing radical.

6. A liquid crystalline copolymer as claimed in claim 3, which contains from 0.5 to 40% by weight, based on the copolymer, of a dye containing radical.

7. A liquid crystalline copolymer which is of the formula ##STR49## where R² is hydrogen or methyl, X is --O-- Y is a chemical bond, A is a linear C₂ -C₂₀ -alkylene group, R³ is ##STR50## R⁵ is C₁ -C₁₂ -alkyl, C₁ -C₁₂ -alkoxy, C₄ -C₁₂ -alkoxycarbonyl, C₁ -C₁₂ -alkanoyloxy, fluorine, chlorine, cyano, phenyl, 4-cyanophenyl or nitro and R⁶ is C₁ -C₁₂ -alkyl, the copolymer containing from 0.5 to 40% by weight, based on the polymer, of a dye containing radical.

8. A liquid crystalline copolymer as claimed in claim 7, which carries various mesogenic groups R³.

9. A liquid crystalline copolymer as claimed in claim 7, wherein A is a group of the formula --(CH₂)₂ --, --(CH₂)₃ --, --(CH₂)₄ --, --(CH₂)₅ --, --(CH₂) ₆ --, --(CH₂)₇ --, --(CH₂)₈ --, --(CH₂)₉ --, --(CH₂)₁₀ --, --(CH₂)₁₁ --, --(CH₂) ₂ --O-- (CH₂)₂ --, --(CH₂)₃ --O--(CH₂)₂ --, ##STR51##

10. A liquid crystalline copolymer as claimed in claim 8, wherein A is a group of the formula --(CH₂)₂ --, --(CH₂)₃ --, --(CH₂)₄ --, --(CH₂)₅ --, --(CH₂) ₆ --, --(CH₂)₇ --, --(CH₂)₈ --, --(CH₂)₉ --, --(CH₂)₁₀ --, --(CH₂)₁₁ --, --(CH₂) ₂ --O--(CH₂)₂ --, --(CH₂)₃ --O--(CH₂)₂ --, ##STR52##

11. A liquid crystalline copolymer as claimed in claim 7, wherein R³ is ##STR53## where R' is C₁ -C₁₂ -alkyl, C₁ -C₁₂ -alkoxy, cyano, phenyl or 4-cyanophenyl and R" is C₁ -C₁₂ -alkyl, and the polymer can carry identical or different mesogenic groups R³.